5-Acetyl-1,2,6-trimethyltricyclo[5,3,2,02,7 ]dodeca-5-ene perfume composition

ABSTRACT

5-Acetyl-1,2,6-trimethyltricyclo[5,3,2,0 2 ,7 ]dodeca-5-ene having the formula (I) ##SPC1## 
     and a process for producing this compound. This compound is useful as a perfume.

This is a division of application Ser. No. 537,002, filed Dec. 27, 1974.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to 5-acetyl-1,2,6-trimethyltricyclo[5,3,2,0²,7]dodeca-5-ene and to a process for producing this compound.

2. Description of the Prior Art

Amber-like fragrant substances are important starting materials for ablended perfume, and, of these substances, ambergris obtainable fromsperm whales is the most expensive. The fragrance component of thisambergris was clarified by E. Lederer and L. Ruzicka in 1946 to be asubstance formed from ambrein which is a triterpenic compound. Eversince, many attempts to synthesize amber-like fragrant substances equalto the natural material, or similar substances have been made. Some ofthem can be utilized as a substitute for expensive ambergris. Forexample, manool derivatives, which are diterpenic compounds and can beobtained from a special needle-leaf tree, are widely used as such asubstitute. However, in general, the amber-like fragrant substances aredifficult to synthesize and moreover, special natural products arerequired as a starting material to synthesize amber-like fragrantsubstances. Therefore, synthetic amber-like fragrant substances areinevitably expensive.

SUMMARY OF THE INVENTION

This invention provides 5-acetyl-1,2,6-trimethyltricyclo[5,3,2,0²,7]dodeca-5-ene having the formula (I) ##SPC2##

which has an excellent wood-like or amber-like fragrance, and a processfor producing 5-acetyl-1,2,6-trimethyltricyclo[5,3,2,0²,7 ]dodeca-5-ene(hereinafter "Compound (I)") comprising acetylating1,2,6-trimethyltricyclo[5,3,2,0²,7 ]dodeca-5-ene (hereinafter "Compound(II)") in the presence of an acid catalyst.

BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS

FIG. 1 is an infrared spectrum of Compound (I) obtained according to thepresent invention.

FIG. 2 is a mass spectrum of Compound (I) obtained according to thepresent invention.

FIG. 3 is an NMR spectrum of Compound (I) obtained according to thepresent invention.

DETAILED DESCRIPTION OF THE INVENTION

Compound (I) produced according to the present invention has themolecular formula, C₁₇ H₂₆ O, and a structure represented by the formula(I) ##SPC3##

According to this invention, Compound (I) can be easily obtained muchmore clearly than conventional amber-like fragrant substances, and isalso of industrial value because of its excellent amber-like fragrance.

In order to achieve the acetylation of Compound (II), for example,Compound (II) is reacted with an acetylating agent such as acetylchloride or acetic anhydride with acetic anhydride being especiallypreferred in the presence of an acid catalyst. The acetylation can becarried out in the presence or absence of a solvent. The molar ratio ofacetic anhydride is generally about 1.1 to 5 moles, preferably 4 molesof acetic anhydride per mole of Compound (II). A suitable amount ofacetyl chloride also is generally about 1.1 to 5 moles of acetylchloride per mole of Compound (II).

Examples of suitable solvents which can be used are preferablyhalogenated hydrocarbons such as carbon tetrachloride, chloroform,methylene chloride, etc., and other solvents, e.g., saturatedhydrocarbons such as hexane octane, etc., ethers such as diethyl ether,dipropyl ether, etc., and the like can also be used. The amount of thesolvent is not particularly limited, but the solvent is generally usedin the range of about 50 to 300% by volume to the volume of Compound(II).

As the acid catalyst, a Friedel-Crafts acid catalyst is preferablyemployed, and suitable examples of Friedel-Crafts acid catalysts includeboron trifluoride, stannic chloride, ferric chloride, zinc chloride,polyphosphoric acid or a mixture of polyphosphoric acid and phosphoricacid, etc. The acid catalyst which can be used can vary in the range offrom about equimolar amount to 1 to 2 mole% to Compound (II). It isgenerally advantageous for a strong acid catalyst such as borontrifluoride to be used at a lower concentration, and for a weak acidcatalyst such as zinc chloride to be used at a higher concentration.

The reaction is carried out at a temperature of about -5° to 100° C,preferably -5° to 85° C. In order to obtain the best results, thepreferred reaction temperatures vary depending upon the kind of acidcatalyst used. For example, when boron trifluoride is used, the reactionis preferably carried out at about 0° C in an ice bath, and when stannicchloride or ferric chloride is used, the reaction is preferably carriedout at a temperature of about 10° to 50° C. Furthermore, when zincchloride or polyphosphoric acid or a mixture of polyphosphoric acid andphosphoric acid is used, the preferred reaction temperature ranges fromabout 70° to 80° C.

The reaction time varies depending upon the kind of solvent, the amountof the solvent used and the reaction temperature, but is suitably about30 minutes to 10 hours. The completion of the reaction can be detectedby gas chromatographic analysis, and therefore, the reaction time can bedetermined by setting the operation conditions.

After completion of the reaction, the reaction solution is diluted withwater, and the remaining acetylating agent is hydrolyzed, followed byextraction with a solvent such as n-hexane, etc. The extracted oilylayer is washed with a basic solution, e.g., a dilute solution of abasic substance such as sodium carbonate, sodium bicarbonate, sodiumacetate, etc., e.g., at a concentration of about 5% by weight, and theresulting acetic acid, the acid catalyst and the like are neutralizedand removed. Thus, the extracted solution is concentrated and distilledunder a reduced pressure to obtain Compound (I).

Compound (II) used as a starting material in the process of thisinvention can be prepared by subjecting1,5,9-trimethylcyclododecatriene-1,5,9 (hereinafter "1,5,9-TMCDT") whichis a cyclic trimer of isoprene to an intramolecular ring closurereaction with an acid catalyst as disclosed in copending U.S. patentapplication Ser. No. 537,004, filed Dec. 27, 1974 (corresponding toJapanese Patent Application Nos. 4207/1974 and 102646/1974) filedsimultaneously herewith.

The thus obtained Compound (I) is a fragrant substance having a richnatural ambergris-like fragrance and a peculiar wood-like odor. WhenCompound (I) is absorbed on a filter paper and allowed to stand in aroom at room temperature (e.g., about 20° to 30° C), the residualfragrance is found to be very strong and to last for over 1 week.

The utility value and application range of Compound (I) are wide as aperfumery material. That is, Compound (I) can be widely used as aperfume, for example, as a component for a rich perfume to a perfume foran inexpensive soap.

The present invention is further illustrated in greater detail byreference to the following Reference Example and Examples, but theexamples are not to be construed as limiting the scope of thisinvention. Unless otherwise indicated, all parts, percents, ratios andthe like are by weight.

REFERENCE EXAMPLE

Into a one liter three-necked flask were charged to 150 g of1,5,9-trimethylcyclododecatriene-1,5,9 (1,5,9-TMCDT) having a meltingpoint of 91° to 92° C, 260 ml of formic acid and 150 ml ofdichloromethane, and these materials were mixed and maintained at atemperature of 5° to 10° C. A mixed solution of 7.5 ml of sulfuric acidand 40 ml of formic acid was then added dropwise thereto over a periodof 30 minutes while keeping the temperature at 5° to 10° C. Theresulting materials were reacted with stirring at that temperature for 3hours, and further reacted with stirring at room temperature (i.e.,about 20° to 30° C) for 3 additional hours. After completion of thereaction, dichloromethane was recovered by distillation, and formic acidwas then distilled off under reduced pressure. The residue wasneutralized and washed with a 3% aqueous sodium bicarbonate solution,and dried with anhydrous sodium sulfate, followed by distillation invacuo, whereby 135 g of the fraction of Compound (II) having a boilingpoint of 75°-80° C/0.05 mmHg was obtained.

As a result of the Ir, NMR and MAS spectra of Compound (II) and also asa result of X-ray crystal structural analysis of a crystalline ketonecompound derived from Compound (II), Compound (II) was determined tohave the structural formula (II) ##SPC4##

EXAMPLE 1

Into a 500 ml four-necked flask equipped with thermometer, a droppingfunnel and a reflux condenser were charged 26 g (0.077 mol) ofpolyphosphoric acid (H₆ P₄ O₁₃) and 27.5 g of phosphoric acid, and thesematerials were maintained at a temperature of 75° to 80° C. 80 g (0.78mol) of acetic anhydride was then added dropwise thereto over a periodof 30 minutes. Subsequently, 41 g of (0.2 mol) of Compound (II) wasadded thereto over a period of 1.5 hours at that temperature, and thesematerials were stirred for 4 hours and cooled to room temperature (i.e.,about 20° to 30° C). 200 ml of water was then added thereto and thecontents were allowed to stand. After extraction with 200 ml ofn-hexane, the extracted solution was washed successively with water, a5% aqueous sodium bicarbonate solution and water, and dried withanhydrous sodium sulfate. Then, the n-hexane was recovered bydistillation, and the residue was distilled under reduced pressure,whereby 42 g of an oily fraction having a boiling point of 110°-115°C/1.5 mmHg was obtained in a yield of 85%.

Refractive Index: n_(D) ²⁵ 1.5253

    ______________________________________                                        Elemental Analysis:                                                                          C        H                                                     ______________________________________                                        Calculated (%):                                                                              82.87    10.64                                                 Found (%):     82.75    10.69                                                 ______________________________________                                    

Ir spectrum:

α,β-Unsaturated ketone characteristic absorption: 1682 cm⁻ ¹

Mas spectrum: M⁺ 246 (molecular ion)

Nmr spectrum: ##STR1##

EXAMPLE 2

Into a 500 ml four-necked flask equipped with a thermometer, a droppingfunnel, a reflux condenser and a stirrer were charged 100 g (0.49 mol)of Compound (II) and 100 g of methylene chloride, and 10 g of stannicchloride was added thereto over a period of one hour at a temperature of25° to 30° C. 200 g (1.96 mols) of acetic anhydride was then added tothe resulting mixture over a period of 2 hours at a temperature of 20°to 30° C, and the mixture was further reacted at a temperature of 22° to28° C for 2 additional hours. The resulting mixture was then treated inthe same manner as described in Example 1, whereby 92.5 g of Compound(I) was obtained in a yield of 77%.

EXAMPLE 3

Into a 500 ml four-necked flask equipped with a stirrer, a thermometer,a reflux condenser and a dropping funnel were charged 135 g of aceticanhydride and 155 ml of a 50% diethyl ether solution of a borontrifluoride-diethyl ether complex salt, and maintained at 0° C. 50 g ofCompound (II) was then added thereto over a period of 2 hours at thattemperature, and the contents were stirred for 2 hours at thattemperature. Subsequently, the resulting mixture was poured into 400 gof ice and a 5% aqueous sodium hydroxide solution was then addedthereto, followed by the same work-up procedures as described inExample 1. Thus, 42.5 g of Compound (I) was obtained in a yield of 71%.

EXAMPLE 4

The following formulation is suitable as a base for a perfume or aneau-de-cologne:

    ______________________________________                                                          g                                                           ______________________________________                                        Civet Absolute      5                                                         Musk Absolute       5                                                         Oak Moth Absolute   30                                                        Vanilla Absolute    10                                                        Musk Ambrette       80                                                        Sandalwood Oil      50                                                        Patchouli Oil       80                                                        Methyl Ionone       30                                                        Vetiver Oil         80                                                        Eugenol             20                                                        Phenylethyl Alcohol 30                                                        Geraniol            30                                                        Benzyl Acetate      30                                                        Jasmine Absolute    20                                                        Hexylcinnamic Aldehyde                                                                            50                                                        Linalool            50                                                        Linalyl Acetate     50                                                        Bergamot Oil        120                                                       Compound (I)        80                                                                            850 g                                                     ______________________________________                                    

EXAMPLE 5

The following formulation is suitable as for a soap perfume:

    ______________________________________                                                          g                                                           ______________________________________                                        Ethylene Brassylate 50                                                        Sandalwood Oil      30                                                        Oak Moth Resinoid   10                                                        Patchouli Oil       30                                                        Coumarin            40                                                        Bornyl Acetate      30                                                        Citronellol         80                                                        Tetrahydrogeraniol  10                                                        Petigrain Oil       15                                                        Lavandine Oil       80                                                        Stearyl Acetate     15                                                        Pineneedle Oil      10                                                        Linalool            170                                                       Linalyl Acetate     130                                                       Compound (I)        100                                                                           800 g                                                     ______________________________________                                    

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A perfume composition containing5-acetyl-1,2,6-trimethyltricyclo[5,3,2,0²,7 ]dodeca-5-ene having theformula (I) ##SPC5##and other perfumery ingredients.